Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research (Ministry of Education, China), College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081, P. R. China.
ACS Sens. 2022 Aug 26;7(8):2465-2474. doi: 10.1021/acssensors.2c01221. Epub 2022 Aug 16.
A novel signal on-off glutathione (GSH) electrochemical sensor was developed based on a AuCu bimetal-decorated Zr-containing metal-organic framework (Zr-MOF), in which a signal amplification strategy promoted by solid-state electrochemistry of cuprous chloride (CuCl) was used. The Zr-MOF with a large surface area can be effectively used as the substrate for the in situ growth of AuCu bimetals to obtain the Zr-MOF@AuCu nanocomposite. The interaction between Cu in Zr-MOF@AuCu and Cl in the solution accompanied with the formation of CuCl displays an enlarged stable oxidation current, which greatly declines with the addition of GSH owing to the specific Cu-GSH interaction. The conversion of CuCl into Cu-GSH triggered the "crowding-out effect" and resulted in a sharp drop in the peak current of CuCl, which can realize the ultrasensitive and selective detection of GSH. The detection mechanism was investigated, and the detection range was 10 pM-1 mM with the detection limit as low as 2.67 pM. The special response mechanism for the detection of GSH allows the highly selective detection of GSH in various real samples with reliable results, endowing the proposed electroanalysis sensor with broad application prospects in biological and food analysis.
基于金铜双金属修饰的含锆金属有机骨架（Zr-MOF），开发了一种新型的谷胱甘肽（GSH）电化学传感器信号开关。该策略利用固态电化学氯化亚铜（CuCl）促进信号放大。具有较大比表面积的 Zr-MOF 可有效用作原位生长金铜双金属的基底，得到 Zr-MOF@AuCu 纳米复合材料。Zr-MOF@AuCu 中 Cu 与溶液中 Cl 的相互作用伴随着 CuCl 的形成，显示出放大的稳定氧化电流，而由于 Cu-GSH 的特殊相互作用，随着 GSH 的加入，该电流会大大降低。CuCl 转化为 Cu-GSH 引发了“拥挤效应”，导致 CuCl 的峰电流急剧下降，从而实现了对 GSH 的超灵敏和选择性检测。研究了检测机制，检测范围为 10 pM-1 mM，检测限低至 2.67 pM。该传感器对 GSH 的特殊响应机制允许在各种实际样品中进行高度选择性的 GSH 检测，结果可靠，为所提出的电化学分析传感器在生物和食品分析中的广泛应用提供了广阔的前景。
